Molecular Diffusion in Gases

Diffusion plus Convection

+
= + ( )

 Molecular Diffusion in Gases
Equimolar Counterdiffusion
In terms of mole fraction,
A B
=

=

A B
 Molecular Diffusion in Gases
Uni-component Diffusion

= +

=

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 Molecular Diffusion in Gases
Example

Water in the bottom of a narrow

metal tune is held a t a constant
temperature of 293 K. The total
pressure of air (assumed dry) is
1.01325 105 Pa and the temperature
is 293 K.
Water evaporates and diffuses through the air in the tube, and the
diffusion path z2-z1 is 0.1524m long. Calculate the rate of evaporation
of water vapor at 293 K and 1 atm pressure. The diffusivity of water
in air is 0.250 x 10-4 m2/s. Assume that the system is isothermal.
Introduction to
Mass Transfer II
 Outline

3. Molecular Diffusion in Gases

Diffusion with Varying Cross-sectional Area
4. Molecular Diffusion in Liquids
5. Molecular Diffusion in Solids
6. Prediction of Diffusivities
 Molecular Diffusion in Gases
Example:
Diffusion through a varying cross-sectional area

A sphere of naphthalene having a radius of 2.0 mm

is suspended in a large volume of still air at 318 K
and 1.01325x105 Pa. The surface temperature of
the naphthalene can be assumed to be at 318 K and
its vapor pressure at 318 K is 0.555 mm Hg. The DAB
of naphthalene in air at 318 K is 6.92x10-6 m2/s.
Calculate the rate of evaporation of naphthalene
from the surface.
 Molecular Diffusion in Gases

Given:

DAB = 6.92x10-6 m2/s

pA1 = (0.555/760)*(101325) =
74.0 Pa
pA2 = 0
r1 = 0.002 m
* The radius of the sphere
=
decreases slowly with time
 Molecular Diffusion in Gases

=


=
( )
Where A = 4 2
Substitution and rearranging,

2
=
4 ( )
 Molecular Diffusion in Gases

2 1
2
=
4 1 ( )
1

The left side of the equation will be

1 1 1
2
= 2 = [ ]
4 4 4 1
1 1
 Molecular Diffusion in Gases

2 1
2
=
4 1 ( )
1

The right side of the equation will be

2 1 1
=
1 2
 Molecular Diffusion in Gases

2 1
2
=
4 1 ( )
1

Solving for the rate of evaporation,

1
= 41 ANS: 4.9 x 10-9 mol/s
2
 Outline

3. Molecular Diffusion in Gases

Diffusion with Varying Cross-sectional Area
4. Molecular Diffusion in Liquids
5. Molecular Diffusion in Solids
6. Prediction of Diffusivities
 Molecular Diffusion in Liquids

Gas Model
Gases are made of
continuous free space
throughout which are
distributed moving
molecules.
For gases,
Kinetic theory is well developed

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 Molecular Diffusion in Liquids

Liquid Model

A continuous phase of
arranged molecules close to
each other but held together
by strong intermolecular forces

Dispersed throughout the

phase are holes of free space
The structure is more complex.
Molecular Diffusion in Liquids

Rate of Diffusion
>

BUT only about 100 times faster.

 Molecular Diffusion in Liquids
Equations for Diffusion
+
= + ( )

1. For equimolarcounterdiffusion, =
where

= = = ( ) + ( )

 Molecular Diffusion in Liquids
Equations for Diffusion
+
= + ( )

2. For unicomponent diffusion, = 0

NOTE:

= (1 + ) + = ( )


( ) average value for the

molar density of the mixture
 Molecular Diffusion in Liquids
Example

An ethanol (A) water (B) solution in the form of a

stagnant film 2.0 mm thick at 293 K is in contact at one
surface with an organic solvent in which ethanol is
soluble and water is insoluble. Hence NB = 0. At point 1
the concentration of ethanol is 16.8 wt% and the
solution density 1 = 972.8 kg/m3. At point 2 ethanol
concentration is 6.8 wt% and 2 = 988.1 kg/m3. The
diffusivity of ethanol is 0.740x10-9 m2/s. Calculate the
steady-state flux NA.
 Outline

3. Molecular Diffusion in Gases

Diffusion with Varying Cross-sectional Area
4. Molecular Diffusion in Liquids
5. Molecular Diffusion in Solids
6. Prediction of Diffusivities
Molecular Diffusion in Solids

What do we expect?

Rate of Diffusion
> >
 Outline

3. Molecular Diffusion in Gases

Diffusion with Varying Cross-sectional Area
4. Molecular Diffusion in Liquids
5. Molecular Diffusion in Solids
6. Prediction of Diffusivities
 Predicting Diffusivities
For gases at low density
- almost independent of concentration
- increase with temperature
- vary inversely with pressure
For liquids and solids,
- strongly concentration-dependent
- generally increase with temperature
 Predicting Diffusivities
Empirical Equations
For gases,
1. See Table 2-324 Perrys
2. Chapman and Enskog Equation

MB = molecular weight of B in kg/kmol

DAB = diffusivity in m2/s
AB = average collision diameter
T = temperature in K
D,AB= collision integral based on
MA = molecular weight of A in kg/kmol
Lennard-Jones potential
 Predicting Diffusivities
Empirical Equations
For gases,
3. Gilliland Equation
1 1
1.38 107 3 ( + )

= 1 1
(3 + 3 )2

DAB = diffusivity
T = temperature
MA = molecular weight
V = molar volume
P= pressure
 Predicting Diffusivities
Empirical Equations
For liquids,
4. See Table 2-325 Perrys
5. Stokes Einstein Equation

4. Wilke and Chang Equation

 Predicting Diffusivities
All diffusivities have units m2/s
Therefore, their ratios are dimensionless groups

Dim. Group Ratio Equation

molecular diffusivity of momentum /
Prandtl, Pr molecular diffusivity of heat

Schmidt, Sc momentum diffusivity/ mass diffusivity


Lewis, Le thermal diffusivity/ mass diffusivity